US4533659A - Microbicidal 2-(1H-1,2,4-triazolylmethyl-1'-yl)-2-siloxy-2-phenyl-acetates - Google Patents

Microbicidal 2-(1H-1,2,4-triazolylmethyl-1'-yl)-2-siloxy-2-phenyl-acetates Download PDF

Info

Publication number
US4533659A
US4533659A US06/499,725 US49972583A US4533659A US 4533659 A US4533659 A US 4533659A US 49972583 A US49972583 A US 49972583A US 4533659 A US4533659 A US 4533659A
Authority
US
United States
Prior art keywords
sub
alkyl
phenyl
substituted
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/499,725
Other languages
English (en)
Inventor
Wolfgang Eckhardt
Walter Kunz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis Corp
Original Assignee
Ciba Geigy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Corp filed Critical Ciba Geigy Corp
Assigned to CIBA-GEIGY CORPORATION reassignment CIBA-GEIGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CIBA-GEIGY AG, A SWISS COMPANY
Application granted granted Critical
Publication of US4533659A publication Critical patent/US4533659A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • the present invention relates to silyloxyalkane azoles of the formula I below and to the agriculturally acceptable acid addition salts and metal complexes thereof.
  • the invention further relates to the preparation of these compounds as well as to agrochemical compositions which contain at least one of the novel compounds as active ingredient.
  • the invention also relates to the preparation of such compositions and to a method of controlling harmful microorganisms or of treating plants to prevent them from attack by such microorganisms.
  • X is the bridge member --CH ⁇ or --N ⁇
  • Ar is a phenyl, diphenyl or naphthyl group
  • R 1 , R 2 and R 3 independently of one another are hydrogen, nitro, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkyl,
  • R is one of the groups --COOR 5 , --COSR 6 , ##STR4## or --CN,
  • R 5 is C 2 -C 10 alkenyl which is unsubstituted or substituted by halogen; C 2 -C 10 alkynyl which is unsubstituted or substituted by halogen; or is a C 3 -C 8 cycloalkyl group or a phenyl group which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, --CN or --CF 3 ; or is a C 1 -C 12 alkyl chain which from C 2 alkyl may be interrupted by oxygen or sulfur and is unsubstituted or substituted by a member selected from the group consisting of halogen, phenyl, --COO--C 1 --C 4 alkyl, --CO--C 1 --C 4 alkyl, --CO-phenyl, an unsaturated or saturated 5- or 6-membered ring containing oxygen or sulfur as heteroatom, with each phenyl moiety being unsubstit
  • R 6 is C 1 -C 10 alkyl, or is a phenyl or benzyl group, each unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, --CN or --CF 3 ,
  • R 7 and R 8 are hydrogen, C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, or a phenyl or benzyl group in each of which the aromatic ring is unsubstituted or substituted by halogen, C 1 -C 4 -alkyl, C 1 -C 4 alkoxy, --CN or --CF 3 , or one of R 7 and R 8 is also the --N(R 9 )(R 10 ) group or both taken together form a 5- or 6-membered saturated or unsaturated heterocyclic ring which may additionally contain 1 or 2 further N atoms,
  • R 9 and R 10 are hydrogen, C 1 -C 4 alkyl or a phenyl radical which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl, --CN or --CF 3 ;
  • R 4 is the --Si(R 11 )(R 12 )(R 13 ) group, wherein each of R 11 , R 12 and R 13 independently is a radical selected from C 1 -C 4 alkyl, C 3 -C 7 alkenyl or phenyl, each unsubstituted or substituted by one or more halogen atoms,
  • alkyl by itself or as moiety of another substituent comprises e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc.
  • Alkenyl is e.g. vinyl, propen-1-yl, allyl, buten-1-yl, buten-2-yl, buten-3-yl etc., as well as chains containing several double bonds.
  • Alkynyl is e.g. propyn-1-yl, propargyl, butyn-1-yl, butyn-2-yl etc., with propargyl being preferred.
  • Haloalkyl is in particular a monohalogenated to perhalogenated alkyl substituent, e.g. CHCl 2 , CH 2 Cl, CCl 3 , CF 3 , CH 2 CH 2 Cl etc. Throughout this specification, halogen denotes fluorine, chlorine, bromine or iodine, with chlorine, bromine or fluorine being preferred.
  • Cycloalkyl is e.g.
  • Haloalkenyl is an alkenyl group which is substituted by one or more halogen atoms, e.g. chlorine and bromine, preferably chlorine.
  • Furyl is preferably 2-furyl, tetrahydrofuryl, preferably 2-tetrahydrofuryl.
  • Pyridyl is preferably pyrid-3- or -4-yl.
  • Naphthyl is ⁇ - or ⁇ -naphthyl, preferably ⁇ -naphthyl.
  • heterocyclic 5- or 6-membered rings containing up to 3 nitrogen atoms are pyrazole, imidazole, 1,2,4-triazole and 1,3,4-triazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine and 1,2,4-triazine.
  • salt-forming acids are inorganic acids, e.g. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, or hydriodic acid, and also sulfuric acid, phosphoric acid, phosphorous acid, nitric acid; and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid.
  • hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, or hydriodic acid, and also sulfuric acid, phospho
  • Metal complexes of the formula I consist of the basic organic molecule and an inoraganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the third and fourth main group of the Periodic Table such as aluminium, tin or lead, and of the first to eighth auxiliary group such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, mercury etc. Preferred elements are those of the auxiliary groups of the fourth period.
  • the metals may exist in different valency states.
  • the metal complexes of the formula I may be mononuclear or polynuclear, i.e. they can contain one or more parts of the organic molecule is ligands. Complexes with copper, znc, manganese and tin are preferred.
  • the compounds of formula I are oils, resins or mainly solids which are stable at room temperature and have very valuable microbicidal properties. They can be used in agriculture or related fields preventively and curatively for controlling phytopathological microorganisms, for which utility the triazolylmethyl derivatives falling within the scope of formula I (X is N) are preferred.
  • the compounds of formula I are very well tolerated by cultivated plants. The development of the plants is not impeded or retarded in any stage.
  • X is the bridge member --CH ⁇ or --N ⁇
  • Ar is a phenyl, diphenyl or naphthyl group
  • R 1 , R 2 and R 3 are hydrogen, nitro, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkyl,
  • R 5 is C 1 -C 4 alkyl, phenyl, or phenyl or benzyl, each substituted by one or more nitro groups, halogen atoms and/or methyl groups,
  • R 4 is the --Si(R 11 )(R 12 )(R 13 ) group, wherein each of R 11 , R 12 and R 13 independently is a radical selected from C 1 -C 4 alkyl, C 3 -C 7 alkenyl or phenyl, each unsubstituted or substituted by one or more halogen-atoms,
  • a further preferred subgroup comprises compounds of formula I, wherein X is the bridge member --CH ⁇ or --N ⁇ ; Ar is a phenyl group; R 1 in the ortho-position is hydrogen, nitro, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, or C 1 -C 3 haloalkyl; R 2 in the para-position is hydrogen, nitro, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkyl; R 3 is hydrogen, methyl or halogen; R is a group --COOR 5 , --COSR 6 , ##STR6## or --CN; R 5 is C 1 -C 4 alkyl, phenyl, or phenyl or benzyl, each substituted by one or more nitro groups, halogen atoms and/or methyl groups; R 6 is C 1 -C 10 alkyl, or phenyl or benzyl, each
  • Yet another particularly preferred subgroup comprises compounds of the formula I, wherein X is the bridge member --N ⁇ ; the grouping ##STR7## is a phenyl group which is substituted in the ortho- and/or para-position by nitro, fluorine, chlorine, bromine, methyl, methoxy and/or CF 3 ; R is the --COOR 5 group; R 5 is C 1 -C 4 alkyl, phenyl, or phenyl or benzyl, each substituted by nitro, chlorine, bromine, fluorine and/or methyl; and R 4 is the --Si(R 11 )(R 12 )(R 13 ) group, wherein each of R 11 , R 12 and R 13 independently is C 1 -C 4 alkyl or halophenyl, each unsubstituted or substituted by halogen; and the acid addition salts and metal complexes thereof.
  • This subgroup will be designated throughout as compounds I***.
  • the compounds of the formula I are prepared by reacting an alcohol of the formula II ##STR8## with a halosilane of the formula III
  • suitable solvents for the reaction are aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum, ether; halogenated hydrocarbons such as chlorobenzene, methylene, chloride, ethylene, chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), anisole, dioxan, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; N,N-dialkylated amides such as dimethylformamide; dimethylsulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with one another.
  • aliphatic and aromatic hydrocarbons such as benzene,
  • Suitable inert gases are e.g. nitrogen, helium, argon or, in certain cases, also carbon dioxide.
  • the yield may also be improved by carrying out the reaction under elevated pressure.
  • Suitable inorganic bases are oxides, hydrides, hydroxides, carbonates, carboxylic acid salts and alcoholates of alkaline earth metals, preferably of alkali metals, in particular those of sodium and potassium (e.g. NaH, NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , CaCO 3 , CH 3 COONa, C 2 H 5 COOK, C 2 H 5 ONa, CH 3 ONa etc.), preferably the alkali metal hydrides such as NaH.
  • Suitable organic bases are trialkylamines, e.g. triethylamine or other tertiary amines such as triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine etc.
  • the intermediates and final products obtained by the preparatory methods of the invention can be isolated from the reaction medium and, if desired, purified by one of the methods conventionally employed, e.g. by extraction, crystallisation, chromatography, distillation etc.
  • Q in formula XV is either a customary leaving group, e.g. halogen, preferably chlorine, bromine or iodine, or is a sulfonyloxy group, preferably a benzenesulfonyloxy, paratosyloxy or lower alkylsulfonyloxy group, preferably a mesyloxy group, or is an acyloxy group such as trifluoroacetyloxy.
  • Q is also a hydroxy group or, according to "Synthesis 1979," pp. 561-569, is the radical ##STR9## wherein R 8 * and R 9 * are organyl radicals, preferably lower alkyl or unsubstituted or substituted phenyl radicals.
  • M is hydrogen or a metal atom, preferably an alkali metal atom, most preferably sodium or potassium.
  • Hal is halogen, preferably chlorine or bromine.
  • Y is halogen, preferably chlorine or bromine, or is a sulfate or sulfonic acid ester group.
  • Az is the following azolyl group ##STR11## wherein X is --CH ⁇ or --N ⁇ . ##STR12##
  • Free ⁇ -hydroxycarboxylic acids of the formula IV are prepared by hydrolysing either, according to equation A, a dioxolanone of the formula V or, according to equation B, a cyanohydrin of the formula VI in basic or acid medium.
  • the hydrolysis reactions A and B are performed with acids or bases, advantageously in aqueous and/or alcoholic solutions, i.e. in polar solvents.
  • the reactions can also be carried out in two-phase media, which case it is advantageous to add a customary phase-transfer catalyst.
  • Inorganic and organic acids are suitable, e.g. mineral acids such as hydrohalic acids, sulfuric acid, phosphoric acid or sulfonic acids (p-toluenesulfonic acid, methanesulfonic acid).
  • Suitable bases are organic and inorganic bases, e.g. oxides, hydrides, hydroxides, carbonates, carboxylic acid salts and alcoholates of alkaline earth metals and alkali metals, especially those of sodium and potassium.
  • reaction temperatures for the ring opening reaction A are in general from 0° to +140° C., preferably from +30° to +80° C., and for the hydrolysis of the cyanohydrin III from +60° to +140° C. preferably from +80° to +120° C., or for both reactions at the boiling point of the solvent or solvent mixture.
  • nitriles VI can be prepared in conventional manner from aryl-azolylmethyl ketones of the formula VII ##STR13## on the lines of a cyanohydrin synthesis, by reaction with HCN or an alkali cyanide, e.g. KCN or NaCN, at 0° to 100° C., advantageously in the presence of a trace of a base (preferably NH 4 OH or gaseous ammonia), or by way of the corresponding NaHSO 3 adduct VII [Org. Syntheses Coll. Vol. I, p. 336, or French patent specification 2,292,706; cf. also Houben Weyl "Methoden der organischen Chemie", Vol. 6/3, p 412].
  • HCN or an alkali cyanide e.g. KCN or NaCN
  • nitriles VI can also be prepared in accordance with J. Org. Chem. 39, p. 914 (1974), by reaction of VII with trimethylsilyl cyanide, in the presence of catalytic amounts of ZnI 2 , and subsequent hydrolysis of the adduct.
  • nitriles may also be prepared by reaction of a ketone VII with a di-lower alkylcyanohydrin of the formula ##STR14## (alkyl is in particular methyl, ethyl or propyl), preferably in an inert solvent, or without a solvent, at 50°-150° C.
  • hydrolysis of the nitriles VI to acid derivatives of the formula IV can be performed by methods similar to known methods, for example with concentrated hydrochloric acid [houben-Weyl "Methoden der organischen Chemie", Vol. VIII, p. 427 ff. (1952)].
  • ketones of formula VII used as intermediates are known from German Offenlegungsschrift No. 2 431 407 or from GB patent specification No. 1 464 224. Ketones of this type can also be obtained by hydrolysis from corresponding ketals, for example from those which are mentioned in any one of the following publications: German Offenlegungschrift specification Nos. 2 610 022, 2 602 770, 2 930 029, 2 930 196 and 2 940 133.
  • Ketones of the formula VII which have not been described can be obtained by one of the aforementioned published methods.
  • Compound of the formula II can be prepared according to equation C, in conventional manner, by esterification of the corresponding acid derivative IV (also in the form of its alkali metal salt) with R 5 --Q (XV) at -20° to +140° C. Aprotic solvents are preferred for this reaction.
  • the direct esterification is advantageously performed with excess alcohol R 5 --OH at 0° to 80° C. in the presence of a mineral acid, or preferably of a Lewis acid such as boron trifluoride etherate.
  • Compounds of the formula II can also be prepared according to equation D from an ⁇ -haloacetate of the formula VII with paraformaldehyde at 0° to 140° C., preferably at 10° to 80° C., and (a) with the desired azole of the formula IX (i.e. imidazole or triazole) in the presence of a base (e.g. NaOH), or (b) with an alkali metal salt of the azole of the formula IX in an anhydrous solvent (e.g. dimethylsulfoxide).
  • a base e.g. NaOH
  • an alkali metal salt of the azole of the formula IX e.g. dimethylsulfoxide
  • the ⁇ -haloacetates of formula VIII can be obtained by conventional esterification of the corresponding acids XIV.
  • Inorganic or organic bases can be added in this reaction [cf. also EP published specification No. 15756].
  • oxiranes of the formula X are obtainable by customary epoxidation (for e.g. H 2 O 2 /aqueous NaOH, peracetic acid) from corresponding alkenyl compounds of the formula XI.
  • Compounds of the formula XI are produced from arylacetates of the formula XII by reaction with oxalates of the formula XIII and formaldehyde in the presence of a base [cf. Helvetica Chimica Acta 30, p.1349 (1947) and German Offenlegungsschrift 2 653 189].
  • Esters of the formula II can also be prepared from acids of the formula IV and dimethylformamide acetal (preferably in excess), the acetal component of which is intended to form the alcoholic part of the ester, in a solvent (e.g. a similar anhydrous alcohol or an ether) at 0° to 160° C. [Angew. Chemie 75, p. 296 (1963) and Helv. Chim. Acta 48, 1747 (1965)].
  • a solvent e.g. a similar anhydrous alcohol or an ether
  • the thioesters of the formula Ic in the 2nd reaction can be obtained from the acids Ib with thioalcohols, in the presence of weak bases (tertiary amines), in aprotic solvents such as CHCl 3 , DMF, dichloromethane, DMSO, at -10° to +120° C., preferably at 0° to +40° C.
  • aprotic solvents such as CHCl 3 , DMF, dichloromethane, DMSO
  • Corresponding mandelic acid amides and mandelic acid hydrazides Id are obtainable from esters (or thioesters) of the formula Ia with excess amine R 7 --NH--R 8 .
  • the compounds of formula I ##STR15## contain a centre of asymmetry (*) vicinal to the aromatic group Ar and to R, and can therefore be obtained in the form of two enantiomers.
  • a mixture of both enantiomers is obtained in the preparation of these compounds. This mixture can be resolved into the optical antipodes in conventional manner.
  • Optically pure antipodes are obtained e.g. in variant B, in which the racemate of the formula IV is converted e.g. with an optically active base into the corresponding salts, which are separated by fractional crystallisation and from which the optically pure acids of the formula IV are obtained.
  • These acids can be converted, as illustrated in variant C, into the optically pure esters of the formula II, which in turn can be converted, as in variant F, into the silylated esters Ia.
  • compounds of the formula I have for practical purposes a very useful microbicidal spectrum against phytopathogenic fungi and bacteria. They have very valuable curative, preventive and systemic properties and can be used for protecting cultivated plants. With the compounds of the formula I it is possible to inhibit or destroy the microorganisms which occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such microorganisms.
  • the compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidomycetes (e.g. the genera Hemileia, Rhizoctonia, Pellicularia, Puccinia); Fungi imperfecti (e.g. Botyrtis, Helminthosporium, Fusarium, Septoria, Cercospora, Piricularia and Alternaria).
  • the compounds of formula I have a systemic action. They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic microorganisms which occur in the soil.
  • the compounds of the invention are also especially well tolerated by plants.
  • the invention also relates to microbicidal compositions and to the use of compounds of the formula I for controlling phytophatogenic microorganisms, especially parasitic fungi, and for the preventive treatment of plants to protect them from attack by such microorganisms.
  • the invention further embraces the preparation of agrochemical compositions which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein.
  • the invention furthermore relates to a method of treating plants, which comprises applying thereto the compounds of the formula I or the novel compositions.
  • Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants:
  • cereals wheat, barley, rye, oats, rice, sorghum and related crops
  • beet sucgar beet and fodder beet
  • drupes pomes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons) fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and
  • the compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds.
  • These compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these prepartions, if desired together with further carriers, surfactants or application-promoting adjuvants customarily employed in the art of formulation.
  • Particularly advantageous adjuvants are phospholipids of vegetable or animal origin. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, binders or fertilisers.
  • the compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable to dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • Advantageous rates of application are normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha.
  • the application of such compositions can be made direct to the plant or parts thereof (foliar application), or to the locus of the plant (soil application), or to the propagation parts, e.g. by seed application.
  • compositions or preparations containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • extenders e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
  • aromatic hydrocarbons preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dio
  • the solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand.
  • suitable nonsorbent carriers are materials such as calcite or sand.
  • pregranulated materials of inorganic or organic nature can be used. e.g. especially dolomite or pulverised plant residues.
  • suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactants will also be understood as comprising mixtures of surfactants.
  • Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
  • so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammoniums salts and contain a C 8 -C 22 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignonsulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
  • These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product.
  • corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
  • Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C 8 -C 22 alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the agrochemical compositions usually contain 0.1 to 99%, preferably 0.1 to 95%, of a compound of the formula I, 1 to 99.9%, preferably 99.8 to 5%, of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.
  • compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
  • further ingredients such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
  • Such agrochemical compositions also constitute an object of the present invention.
  • Emulsions of any required concentration can be produced from such concentrates by dilution with water.
  • the active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
  • Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.
  • the active ingredient is thoroughly mixed with the adjuvants and the mixtures is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
  • Wheat plants are treated 6 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06%). After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95-100% relative humidity and about 20° C. and then stood in a greenhouse at about 22° C. Evaluation of rust pustule development is made 12 days after infection.
  • Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.006% based on the volume of the soil). After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The plants are then incubated for 48 hours at 95-100% relative humidity and about 20° C. and then stood in a greenhouse at about 22° C. Evaluation of rust pustule development is made 12 days after infection. Attack on untreated and infected control plants is 100%. Plants treated with compositions containing compounds of formula I exhibit only insignificant ( ⁇ 20%) or no attack. Compounds 1.1, 1.3, 1.8, 1.17, 1.19 to 1.25, 1.32, 1.34 to 1.37, 1.39, 1.45, 1.48. 1.51, 1.53, 1.64, 1.66 and 1.67 completely inhibit fungus attack (0-5%). Compound 1.1 still inhibits fungus attack completely even when used in a concentration of 0.002%.
  • Groundnut plants 10-15 cm in height are sprayed with a wettable powder containing 0.006% of active ingredient and infected 48 hours later with a conidia suspension of the fungus.
  • the infected plants are incubated for 72 hours at about 21° C. and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection, and is based on the number and size of the specks.
  • Barley plants about 8 cm in height are sprayed with a spray mixture (0.02%) prepared from the active ingredient formulated as a wettable powder.
  • the treated plants are dusted with conidia of the fungus after 3-4 hours.
  • the infected barley plants are then stood in a greenhouse at about 22° C. The extent of the infestation is evaluated after 10 days.
  • Barley plants about 8 cm in height are treated with a spray mixture (0.006%, based on the volume of the soil) prepared from the active ingredient formulated as wettable powder. Care is taken that the spray mixture does not come in contact with the parts of the plants above the soil.
  • the treated plants are infected 48 hours later with a conidia suspension of the fungus.
  • the infected barley plants are then stood in a greenhouse at about 22° C. and evaluation of infestation is made after 10 days.
  • Compounds of formula I and compounds of Tables 1 to 4 reduce fungus attack to less than 20%, whereas attack is 100% on untreated and infected control plants.
  • Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient with a conidia suspension of the fungus.
  • the plants are then incubated for 5 days at 90-100% relative humidity and stood in a greenhouse for a further 10 days at 20°-24° C.
  • Scab infestation is evaluated 15 days after infection.
  • Compounds 1.3, 1.8 and 1.25 and others inhibit infestation to less than 10% and completely (e.g. compound 1.3).
  • Shoots on apple trees in field trials are protected to the same extent without being inhibited in their development.
  • Bean plants about 10 cm in height are sprayed with a spray mixture (0.02% concentration) prepared from the active ingredient formulated as wettable powder. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 2 to 3 days at 95-100% relative humidity and 21° C., and evaluation of the fungus attack is then made. Comounds of Tables 1 to 4 inhibit fungus infection very strongly in many cases. At a concentration of 0.02%, compounds 1.1, 1.3, 1.8, 1.19, 1.20, 1.21, 1.22, 1.24, 1.25, 1.32, 1.34, 1.35, 1.36, 1.37, 1.39, 1.45, 1.66 and 1.67 are fully effective (attack 0-5%).
  • rice plants After being reared for 2 weeks, rice plants are sprayed with a spray mixture (0.02%) prepared from a wettable powder formulation of the test compound.
  • the treated plants are infected 48 hours later with a conidia suspension of the fungus.
  • Fungus attack is evaluated after incubation for 5 days at 95-100% relative humidity and 24° C.
  • compounds of Tables 1 to 4 inhibit fungus infestation significantly, e.g. compounds 1.1, 1.8, 1.19, 1.20, 1.22, 1.24, 1.25, 1.35 and 1.66.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
US06/499,725 1982-06-09 1983-05-31 Microbicidal 2-(1H-1,2,4-triazolylmethyl-1'-yl)-2-siloxy-2-phenyl-acetates Expired - Fee Related US4533659A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH355882 1982-06-09
CH3558/82 1982-06-09

Publications (1)

Publication Number Publication Date
US4533659A true US4533659A (en) 1985-08-06

Family

ID=4258577

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/499,725 Expired - Fee Related US4533659A (en) 1982-06-09 1983-05-31 Microbicidal 2-(1H-1,2,4-triazolylmethyl-1'-yl)-2-siloxy-2-phenyl-acetates

Country Status (10)

Country Link
US (1) US4533659A (xx)
EP (1) EP0096660B1 (xx)
JP (1) JPS5931766A (xx)
AT (1) ATE16936T1 (xx)
AU (1) AU564607B2 (xx)
BR (1) BR8303032A (xx)
CA (1) CA1204761A (xx)
DE (1) DE3361481D1 (xx)
ES (1) ES8407497A1 (xx)
ZA (1) ZA834174B (xx)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111032631A (zh) * 2017-11-13 2020-04-17 株式会社吴羽 唑衍生物、中间体化合物及唑衍生物的制造方法，以及农业园艺用药剂以及工业用材料保护剂
CN113727606A (zh) * 2019-04-19 2021-11-30 株式会社吴羽 农业园艺用杀菌剂、植物病害防治方法以及植物病害防治用制品

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU212458B (en) * 1993-09-23 1996-06-28 Richter Gedeon Vegyeszet New silyloxypropane derivatives substituted with triazole or imidazole pharmaceutical compositions containing them and process for producing them
DE4412332A1 (de) * 1994-04-11 1995-10-12 Bayer Ag Silyloxy-cyclopropyl-azolyl-Derivate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4005083A (en) * 1974-05-17 1977-01-25 Bayer Aktiengesellschaft Metal complexes of azolyl ethers
US4291044A (en) * 1978-10-28 1981-09-22 Bayer Aktiengesellschaft Combating fungi with 1-(azol-1-yl)-2-substituted-alken-3-ones
US4366152A (en) * 1977-06-03 1982-12-28 Bayer Aktiengesellschaft Combatting fungi with metal salt complexes of 1-phenyl-2-(1,2,4-triazol-1-yl)-ethanes
EP0086173A1 (de) * 1982-01-15 1983-08-17 Ciba-Geigy Ag Fungizid wirkende und den Pflanzenwuchs regulierende Triazolcarbinolderivate

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2944223A1 (de) * 1979-11-02 1981-05-27 Basf Ag, 6700 Ludwigshafen Fungizide entriazole, ihre herstellung und verwendung
CH647513A5 (de) * 1979-11-13 1985-01-31 Sandoz Ag Triazol-derivate, deren herstellung und verwendung.
DE3000140A1 (de) * 1980-01-04 1981-07-09 Basf Ag, 6700 Ludwigshafen Fungizide azolyl-silyl-glykolether, ihre herstellung und verwendung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4005083A (en) * 1974-05-17 1977-01-25 Bayer Aktiengesellschaft Metal complexes of azolyl ethers
US4366152A (en) * 1977-06-03 1982-12-28 Bayer Aktiengesellschaft Combatting fungi with metal salt complexes of 1-phenyl-2-(1,2,4-triazol-1-yl)-ethanes
US4291044A (en) * 1978-10-28 1981-09-22 Bayer Aktiengesellschaft Combating fungi with 1-(azol-1-yl)-2-substituted-alken-3-ones
EP0086173A1 (de) * 1982-01-15 1983-08-17 Ciba-Geigy Ag Fungizid wirkende und den Pflanzenwuchs regulierende Triazolcarbinolderivate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Eckhardt et al., Chem. Abst. 101: 7423c. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111032631A (zh) * 2017-11-13 2020-04-17 株式会社吴羽 唑衍生物、中间体化合物及唑衍生物的制造方法，以及农业园艺用药剂以及工业用材料保护剂
US10945434B2 (en) 2017-11-13 2021-03-16 Kureha Corporation Azole derivative, intermediate compound, method for producing azole derivative, agricultural or horticultural chemical agent, and protective agent for industrial material
CN111032631B (zh) * 2017-11-13 2021-05-07 株式会社吴羽 唑衍生物、中间体化合物及唑衍生物的制造方法，以及农业园艺用药剂以及工业用材料保护剂
CN113727606A (zh) * 2019-04-19 2021-11-30 株式会社吴羽 农业园艺用杀菌剂、植物病害防治方法以及植物病害防治用制品
CN113727606B (zh) * 2019-04-19 2023-08-15 株式会社吴羽 农业园艺用杀菌剂、植物病害防治方法以及植物病害防治用制品

Also Published As

Publication number Publication date
ES523101A0 (es) 1984-10-01
EP0096660B1 (de) 1985-12-11
ZA834174B (en) 1984-03-28
ES8407497A1 (es) 1984-10-01
DE3361481D1 (en) 1986-01-23
BR8303032A (pt) 1984-01-31
AU1544083A (en) 1983-12-15
JPS5931766A (ja) 1984-02-20
EP0096660A1 (de) 1983-12-21
AU564607B2 (en) 1987-08-20
CA1204761A (en) 1986-05-20
ATE16936T1 (de) 1985-12-15

Similar Documents

Publication Publication Date Title
US4705790A (en) N-(2-nitrophenyl)-4-aminopyrimidine microbicides
US4694009A (en) Pesticidal compositions
CA1210404A (en) 1-carbonyl-1-phenyl-2-azolylethanol-derivatives
US4705800A (en) Difluorbenzodioxyl cyanopyrrole microbicidal compositions
US4659363A (en) N-(2-nitrophenyl)-2-aminopyrimidine derivatives, the preparation and use thereof
US4980355A (en) Compositions for protecting plants against disease
US4663463A (en) Mandelic acid derivatives and mandelonitriles, processes for producing them, and their use for combating microorganisms
US4546099A (en) N-Aminomethyl-3-phenyl-4-cyanopyrrole derivatives, compositions and use thereof as microbicides
US4690942A (en) 1-aryl-2-fluoro-2-azolyl alkanones, alkanols, esters, and ethers, composition containing them, and use of them to control phytopathogenic microorganisms
US4940481A (en) Microbicidal and growth regulating compositions
US4610716A (en) Fluorinated azolyl ethanol growth regulators and microbicides
US4533659A (en) Microbicidal 2-(1H-1,2,4-triazolylmethyl-1'-yl)-2-siloxy-2-phenyl-acetates
JPH0463071B2 (xx)
GB2101994A (en) Microbidical and growth regulating 2-hydroxy-3-azolylpropane derivatives
US5439912A (en) 2-phenylamino-4-cyano-pyrimidines
US4762826A (en) Microbicides
CA1195988A (en) Azolyl-thioether derivatives, processes for their preparation, and their use as fungicides and plant growth regulators
US5068359A (en) Microbicidal compositions
US5015649A (en) Plant-protective compositions
US4517194A (en) Azolylmandelic acid derivatives and use thereof for controlling microorganisms
US4840662A (en) N-(2-nitrophenyl)-5-aminopyrimidine derivatives and useful for controlling harmful micro-organisms
GB2103210A (en) Microbiodical and growth regulating substituted 2-hydroxy-3- azolyl-propane derivatives
US4758670A (en) Microbicidal and growth-regulating compositions
US4940806A (en) Microbicides
AU5883894A (en) Pyrazolyl acrylic acid derivatives, intermediates thereto, and their use as microbicides

Legal Events

Date Code Title Description
AS Assignment

Owner name: CIBA-GEIGY CORPORATION 444 SAW MILL RIVER ROAD, AR

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CIBA-GEIGY AG, A SWISS COMPANY;REEL/FRAME:004387/0045

Effective date: 19850402

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19930808

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362